Systematic monitoring of surface waters in the area of abandoned mine sites constitutes an essential step in the characterisation of pollution from historic mine sites. The analytical data collected throughout a hydrologic period can be used for hydrological modelling and also to select appropriate preventive and/or corrective measures in order to avoid pollution of watercourses. Caudal River drains the main abandoned Hg mine sites (located in Mieres and Pola de Lena districts) in Central Asturias (NW Spain). This paper describes a systematic monitoring of physical and chemical parameters in eighteen selected sampling points within the Caudal River catchment. At each sampling station, water flow, pH, specific conductance, dissolved oxygen, salinity, temperature, redox potential and turbidity were controlled "in situ" and major and trace elements were analysed in the laboratory. In the Hg-mineralised areas, As is present in the form of As-rich pyrite, realgar and occasionally arsenopyrite. Mine drainage and leachates from spoil heaps exhibit in some cases acidic conditions and high As contents, and they are incorporated to Caudal River tributaries. Multivariate statistical analysis aids to the interpretation of the spatial and temporary variations found in the sampled areas, as part of a methodology applicable to different environmental and geological studies. (C) 2009 Elsevier B.V. All rights reserved.